Silicone composition which can be crosslinked into an elastomer by hydrosilylation in the presence of carbene-based metal catalysts, and catalysts of this type

ABSTRACT

This invention relates to silicone compositions which can be crosslinked, preferably into elastomers, by hydrosilylation of at least one PolyOrganoSiloxane -A- carrying unsaturated bonds, using at least one polyorganohydrosiloxane —B— in the presence of a carbene-based metal catalyst —C— as defined in the description and which optionally comprises at least one inhibitor -D- of the hydrosilylation reaction.

CROSS-REFERENCE TO RELATED APPLICATION

This application is the U.S. national stage of International Appln. No. PCT/EP02/07457, filed May 23, 2002, said application being incorporated by reference herein in its entirety relied upon.

The invention relates to the catalysis of hydrosilylation reactions of ethylenically and/or acetylenically unsaturated compounds (for example, olefins or acetylenic derivatives), in particular those involving polyorganosiloxanes (POSs) carrying Si—H units and POSs carrying Si-(ethylenic or acetylenic unsaturation) units.

More specifically, the invention relates to silicone compositions which can be crosslinked (preferably into elastomers) by hydrosilylation of at least one PolyOrganoSiloxane -A- (POS) carrying unsaturated bonds using at least one polyorganohydrosiloxane —B— in the presence of a metal catalyst —C— and which optionally comprise at least one inhibitor -D- of the hydrosilylation reaction.

Hydrosilylation reactions which make it possible for silicones to crosslink are conventionally catalysed by platinum catalysts (U.S. Pat. No. 2,823,218, U.S. Pat. No. 2,970,150). In practice, to date, the majority of industrial hydrosilylation reactions are catalysed by the Karstedt solution, which is composed of platinum complexes in which the platinum is in the 0 oxidation state.

The very high catalytic activity of this type of catalyst, even at ambient temperature, is a major disadvantage in the context of its use in polyaddition HCEs as the crosslinking of the elastomer begins as soon as all the components are brought into contact.

The document WO 01/42558 discloses in particular metal complexes of use as hydrosilylation catalysts, of formula:

in which:

R₃ represents a hydrogen atom; a (C₁-C₈)alkyl group; or a (C₃-C₈)cycloalkyl group;

T₁ and T₂ are identical and represent (C₁-C₈)alkyl or (C₃-C₈) cycloalkyl;

R_(d) and R_(e) are identical and represent (C₁-C₈)alkyl or (C₃-C₈) cycloalkyl.

According to this application, the catalysts are employed for the catalysis of the reaction of a compound comprising an unsaturated bond with a compound exhibiting at least one ≡S—H unit.

Patent U.S. Pat. No. 5,728,839 itself also discloses metal/carbene complexes with heterocyclic carbenes; they are described as being able to be of use as catalysts for the hydrogenation or hydroformylation of unsaturated organic compounds. There is no mention of the crosslinking of silicones in this document.

In point of fact, it might be advantageous to have available, in the field of crosslinkable silicones (in particular those which can be crosslinked into elastomers), catalysts which are active under hot conditions and inactive or virtually inactive at ambient temperature. This would make it possible to formulate single-component silicone compositions which can be crosslinked under hot conditions and which are stable on storage for lengthy periods of time at ambient temperature (pot life). Single-component silicone compositions are those which comprise, in the same mixture, all the reactive entities (Si-Vinyl POS/Si-H POS) and the catalyst. Conventionally, crosslinking inhibitors are used to increase the pot life of single-component silicone compositions. Thus, with the Karstedt catalyst, the use of an inhibitor is essential and makes it possible to change, for example, the stability at ambient temperature of an Si-Vinyl POS/Si-H POS composition from 1 min to 24 H.

Objectives

In such a state of the art, one of the essential objectives of the invention is to provide a silicone composition which can be crosslinked by hydrosilylation and which comprises, as catalyst, one or more metal complexes based on heterocyclic carbenes, this catalyst having a low activity at ambient temperature, so as to make possible the preparation of single-component compositions comprising the catalyst and compounds capable of reacting under hot conditions by hydrosilylation of unsaturated units, while being stable at ambient temperature for lengthy periods (e.g. 1 d to a few months).

Another essential objective of the invention is to provide a silicone composition which can be crosslinked by hydrosilylation and which comprises, as catalyst, one or more metal complexes based on heterocyclic carbenes, this composition not being the site, during crosslinking, of isomerization side reactions or of colorations capable of interfering with the hydrosilylation.

Another essential objective of the invention is to provide novel metal complexes based on heterocyclic carbenes which can be used as hydrosilylation catalysts, the latter having to be highly active under hot conditions and inactive or virtually inactive at ambient temperature, so as to be able to formulate single-component silicone compositions which can be crosslinked under hot conditions and which are stable on storage for lengthy periods of time at ambient temperature (pot life), this being achieved with little or no crosslinking inhibitor.

Another essential objective of the invention is to provide a hydrosilylation process and in particular a process for the hydrosilylation of ethylenically and/or acetylenically unsaturated compounds in the presence of a catalyst comprising the novel metal complexes targeted above.

These objectives are achieved by the present invention, which relates, first, to a silicone composition which can be crosslinked by hydrosilylation of at least one PolyOrganoSiloxane -A- (POS) carrying unsaturated bonds [example: ethylenic and/or acetylenic unsaturation(s)] using at least one polyorganohydro-siloxane —B— in the presence of a metal catalyst —C— and which optionally comprises at least one inhibitor -D- of the hydrosilylation reaction;

-   -   characterized in that the catalyst —C— comprises at least one         compound selected from the products of formula (I):

in which:

-   -   M represents a metal chosen from the metals of Group 8 of the         Periodic Table as published in the Handbook of Chemistry and         Physics, 65th edition, 1984-1985;     -   L_(γ) represents a carbene of formula (II):

in which:

-   -   A and B, which are identical or different, represent C or N, it         being understood that, when A represents N, then T₄ does not         represent anything and, when B represents N, then T₃ does not         represent anything;     -   T₃ and T₄ independently represent a hydrogen atom; an alkyl         group; a cycloalkyl group optionally substituted by alkyl or         alkoxy; an aryl group optionally substituted by alkyl or alkoxy;         an alkenyl group; an alkynyl group; or an arylalkyl group in         which the aryl part is optionally substituted by alkyl or         alkoxy; or else     -   T₃ and T₄ can together and with A and B, when the latter each         represent a carbon atom, form an aryl;     -   T₁ and T₂ independently represent an alkyl group; an alkyl group         optionally substituted by alkyl; a perfluorinated alkyl group or         an alkyl group optionally substituted by a perfluoroalkyl group;         a cycloalkyl group optionally substituted by alkyl or alkoxy; an         aryl group optionally substituted by alkyl or alkoxy; an alkenyl         group; an alkynyl group; or an arylalkyl group in which the aryl         part is optionally substituted by alkyl or alkoxy; or else     -   T₁ and T₂ independently represent a monovalent radical of         following formula (V):         V₁-V₂   (V), in which:         -   V₁ is a divalent hydrocarbonaceous radical, preferably an             alkylene,         -   V₂ is a monovalent radical chosen from the group of the             following substituents:             -   alkoxy, —OR^(o) with R^(o) corresponding to hydrogen,                 alkyl or aryl,             -   amine, preferably N(R^(o))₂ with R^(o) corresponding to                 hydrogen, alkyl or aryl;     -   T₁ and T₂ independently represent a monovalent radical of         following formula (W):         W₁-ω-W₂   (W)         -   in which:         -   W₁ is a divalent hydrocarbonaceous radical, preferably a             linear or branched C₁-C₁₀ alkylene, which is optionally             substituted;         -   ω represents:             —R¹C═CR¹—         -   with R¹ corresponding to H or alkyl,         -   or             —C≡C—;         -   W₂ is a monovalent radical chosen from the group of the             following substituents:         -   R²=alkyl or H;         -   Si-alkyl or Si-alkoxy, preferably —Si(R³)₃ with R³=alkyl;         -   alcohol, preferably —C(R⁴)₂OH with R⁴═H or alkyl;         -   ketone, preferably

with R⁵=alkyl;

-   -   -   carboxyl, preferably

with R⁶=alkyl;

-   -   -   amide, preferably

with R⁷═H or alkyl;

-   -   -   acyl, preferably

with R⁸=alkyl;

-   -   -   or else

    -   the substituents T₁, T₂, T₃ and T₄ can form in pairs, when they         are situated at two adjacent points in the formula (II), a         saturated or unsaturated hydrocarbonaceous chain;

    -   and with the condition that at least one substituent T₁ and/or         T₂, which are identical or different, represent(s) a monovalent         radical of following formula (V):         Z₁-Z₂   (V)         -   in which:         -   Z₁ is a divalent hydrocarbonaceous radical, preferably an             alkylene,         -   Z₂ is a monovalent radical chosen from:             -   a (C₅-C₃₀)cycloalkyl radical comprising at least one                 heteroatom in the ring, preferably nitrogen,             -   a (C₆-C₃₀)aryl radical comprising at least one                 heteroatom in the aromatic ring, preferably nitrogen,

    -   L_(α) and L_(β) are ligands which are identical to or different         from one another and

    -   each represent:

-   -   with, in these formulae (III.1) and (III.2):     -   Z¹, Z², Z³, Z⁴, Z⁵ and Z⁶     -   each independently representing:     -   a. hydrogen,     -   b. a halogen,     -   c. a cyano,     -   d. a saturated or unsaturated, electron-withdrawing or         non-electron-withdrawing, hydrocarbonaceous group, preferably         unsaturated adjacent to the double or triple bond,     -   e. it being possible for two vicinal Z¹ to Z⁶ groups together to         form an electron-withdrawing or non-electron-withdrawing ring         which is advantageously other than the carbene L_(γ) of         formula (II) and which optionally comprises heteroatoms         (preferably O, N or S);         -   or together form the ligand L_(δ) of formula (IV):

-   -   -   in which:         -   Y₁ and Y₂ represent, independently of one another,             CR_(a)R_(b) or SiR_(c)R_(d);         -   X represents O, NR_(e) or CR_(f)R_(g);         -   R¹⁰, R¹¹, R¹³ and R¹⁴, which are identical or different, are             chosen from a hydrogen atom, an alkyl group or an aryl group             optionally substituted by alkyl;         -   R⁹, R¹², R_(a), R_(b), R_(c) and R_(d) are chosen             independently from a hydrogen atom; an alkyl group; an acyl             group; an aryl group optionally substituted by alkyl; a             cycloalkyl group optionally substituted by alkyl; and an             arylalkyl group in which the aryl part is optionally             substituted by alkyl;         -   R_(c) and R_(d) are chosen independently from alkyl; aryl             optionally substituted by alkyl; cycloalkyl optionally             substituted by alkyl; and arylalkyl in which the aryl part             is optionally substituted by alkyl; or else         -   when Y₁ and Y₂ independently represent SiR_(c)R_(d), two             R_(c) groups bonded to two separate silicon atoms together             form a chain of formula:

-   -   -   -   in which n is an integer from 1 to 3; X is as defined                 above; R and R′, which are identical or different, take                 any one of the meanings given above for R_(e), it being                 understood that, when n is 2 or 3, only one silicon atom                 of the said chain may be substituted by one or two                 alkenyl or alkynyl groups; or else             -   when Y₁ and Y₂ independently represent SiR_(c)R_(d), two                 R_(c) groups bonded to separate silicon atoms together                 form a saturated hydrocarbonaceous chain, the two R_(c)                 groups forming, together with the said silicon atoms and                 X, a 6- to 10-membered ring; or else             -   when Y₁ and Y₂ independently represent CR_(a)R_(b), two                 R_(a) groups bonded to separate carbon atoms together                 form a saturated hydrocarbonaceous chain, the two R_(a)                 groups forming, together with the carbon atoms which                 carry them and X, a 6- to 10-membered ring; and             -   R_(f) and R_(g) represent, independently of one another,                 a hydrogen atom; an alkyl group; an acyl group; an aryl                 group optionally substituted by alkyl; a cycloalkyl                 group optionally substituted by alkyl; an arylalkyl                 group in which the aryl part is optionally substituted                 by alkyl; a halogen atom; an alkenyl group; an alkynyl                 group; or an SiG₁G₂G₃ group where G₁, G₂ and G₃ are,                 independently of one another, alkyl; alkoxy; aryl                 optionally substituted by alkyl or alkoxy; or arylalkyl                 in which the aryl part is optionally substituted by                 alkyl or alkoxy.

The presence of specific metal/heterocyclic carbene complexes in the compositions according to the invention confers great stability on the latter in an ambient atmosphere under standard temperature, humidity and pressure conditions. Such silicone compositions can be stored in the single-component form, in the uncrosslinked state, in an ambient atmosphere, for long periods of time (for example, from 1 to several months). This result is all the more advantageous and surprising since, with some metal/heterocyclic carbene catalysts, it is possible to dispense with the use of crosslinking inhibitors or, at the very least, to use less thereof, which is entirely beneficial economically and with regard to limiting the negative repercussions on the crosslinking of the elastomer and its final qualities.

This stability goes together with the ability which the compositions according to the invention have to crosslink under hot conditions (for example from 100° C.) by hydrosilylation into elastomers of good quality, in particular at the structural and mechanical level. In addition, the kinetics of the reaction are satisfactory.

These single-component silicone compositions, which have a long pot life at ambient temperature, are all the more advantageous because their cost is not prohibitive. This advantage is even more marked when they do not comprise an inhibitor.

The definition of the metal complexes of formula (I) constituting the catalyst —C—, an essential compound of the composition according to the invention, is completed below.

The metals of Group 8 represented by M in the formula (I) are, for example, palladium, platinum or nickel in the zero oxidation state. In practice, M represents platinum in the 0 oxidation state.

The term “alkyl” denotes a saturated, linear or branched, hydrocarbonaceous chain which is optionally substituted (e.g. by one or more alkyls), preferably with from 1 to 10 carbon atoms.

Examples of alkyl groups are in particular methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl or n-pentyl.

The alkyl part of the alkoxy radical is as defined above.

The term “cycloalkyl” is understood to mean a saturated, mono- or polycyclic, preferably mono- or bicyclic, hydrocarbonaceous radical preferably exhibiting from 3 to 10 carbon atoms.

The term “saturated polycyclic hydrocarbonaceous radical” is understood to mean a radical exhibiting two or more rings attached to one another via σ bonds and/or condensed in pairs.

Examples of polycyclic cycloalkyl groups are adamantyl and norbornyl.

Examples of monocyclic cycloalkyl groups are cyclopentyl and cyclohexyl.

The term “perfluorinated alkyl” denotes an alkyl comprising at least one perfluoroalkyl group preferably having the formula: —(CH₂)_(p)—C_(q)F_(2q+1)

-   -   in which p represents 0, 1, 2, 3 or 4; q is an integer from 1 to         10; and C_(q)F_(2q+1) is linear or branched.

The expression “aryl” denotes a monocyclic or polycyclic, preferably monocyclic or bicyclic, aromatic hydrocarbonaceous group having from 6 to 18 carbon atoms. It should be understood that, in the context of the invention, the term “polycyclic aromatic radical” is understood to denote a radical exhibiting two or more aromatic nuclei condensed (ortho-condensed or ortho- and peri-condensed) with one another.

The said aromatic hydrocarbonaceous (“aryl”) group is optionally substituted, for example by one or more C₁-C₃ alkyls, one or more halogenated hydrocarbonaceous radicals (e.g. CF₃), one or more alkoxys (e.g. CH₃O) or one or more hydrocarbonaceous radicals comprising one or more ketone units (e.g. CH₃CO—).

Mention may be made, as examples of aryl, of the phenyl and naphthyl radicals.

The expression “arylalkyl” denotes an alkyl group as defined above substituted on its hydrocarbonaceous chain by one or more aryl groups, the aryl group being as defined above. Examples thereof are benzyl and triphenylmethyl.

The term “acyl” is understood to denote an R^(o)—CO— group where R^(o) represents an alkyl as defined above; or else an Ar—CO— group where Ar represents an aryl group as defined above; or else an arylalkyl in which “aryl” and “alkyl” are as defined above and in which the aryl part is optionally substituted, e.g. by an alkyl.

The term “alkenyl” is understood to denote an unsaturated, substituted or unsubstituted, linear or branched, hydrocarbonaceous chain exhibiting at least one olefinic double bond and more preferably a single double bond. Preferably, the alkenyl group exhibits from 2 to 8 carbon atoms, better still from 2 to 6. This hydrocarbonaceous chain optionally comprises at least one heteroatom, such as O, N or S. Preferred examples of alkenyl groups are the allyl and homoallyl groups.

The term “alkynyl” is understood to denote, according to the invention, an unsaturated, substituted or unsubstituted, linear or branched, hydrocarbonaceous chain exhibiting at least one acetylenic triple bond and more preferably a single triple bond. Preferably, the alkynyl group exhibits from 2 to 8 carbon atoms, better still from 2 to 6 carbon atoms. Mention may be made, by way of examples, of the acetylenyl group and the propargyl group. This hydrocarbonaceous chain optionally comprises at least one heteroatom, such as O, N or S.

The expression “does not represent anything” means that the -T₃ and -T₄ substituents respectively do not exist. This is because, in the formula (II), the nitrogen atom is trivalent, so that, when A or B represents N, the nitrogen atom cannot have an additional substituent.

Preferably, in the carbene ligands of formula (II):

(i) T₃ and T₄ represent a hydrogen atom or together form a phenyl,

and/or

(ii) T₁ and T₂, which are identical or different, represent(s) a monovalent radical of following formula (V): *Z₁-Z₂   (V)

in which:

-   -   Z₁ is a divalent hydrocarbonaceous radical, preferably an         alkylene,     -   Z₂ is a monovalent radical chosen from:         -   a (C₅-C₃₀)cycloalkyl radical comprising at least one             heteroatom in the ring, preferably nitrogen,         -   a (C₆-C₃₀)aryl radical comprising at least one heteroatom in             the aromatic ring, preferably nitrogen,

and/or

(iii) A and B both represent a carbon atom.

The ligands L_(α) and L_(β) of the catalyst —C— of formula (I) belonging to the composition according to the invention can independently represent an alkyne of formula (III.1) or an alkene of formula (III.2) substituted by Z¹ to Z⁶ radicals carrying at least one electron-withdrawing unit active with respect to π unsaturation of L_(α) and L_(β), in order to promote the liganding with the metal M of the complex.

Advantageously, in the formulae (III.1) and (III.2), the electron-withdrawing residues are chosen from the group consisting of:

in which:

R₁₇, R₁₈, R₁₉ and R₂₀, which are identical or different, are substituted or unsubstituted alkyl, alkenyl or alkynyl and n′ is between 1 and 50.

Mention may be made, by way of examples of Z¹ to Z⁶ radicals, of:

-   -   those selected from the group consisting of:         —CN, —COOCH₃, —COOCH₂CH₃, —CONC₁₂H₂₅     -   and, in the cases where the Z¹ and Z² substituents form in pairs         and with the triple bond, in (III.1), a ring Cy1 and where Z³ to         Z⁶ form in pairs, with or without the double bond, in (III.2), a         ring Cy2, these rings Cy1 and Cy2 are independently and         preferably chosen from the group consisting of the following         rings:

When L_(α) and L_(β) together form a ligand L_(δ) of formula (IV), the latter is preferably of the type of those in which Y₁ and Y₂ either both represent CR_(a)R_(b) or both represent SiR_(c)R_(d), so that the said complexes either have the formula (IV.1) or have the formula (IV.2):

where: the two R_(a) groups, the two R_(b) groups, the two R_(c) groups and the two R_(d) groups are identical to one another and R⁹═R¹²; R¹⁰═R¹⁴; and R¹¹═R¹³. Preferably, X═O.

According to an alternative form, the two R_(c) groups in (IV.2) together form (a) either a chain

in which n is an integer from 1 to 3; X is as defined above; and R and R′, which are identical or different, take any one of the meanings given above for R_(d), it being understood that, when n is 2 or 3, only one silicon atom of the said chain may be substituted by one or two alkenyl or alkynyl groups;

(b) or a saturated hydrocarbonaceous chain, so that the two R_(c) substituents form, together with the two silicon atoms which carry them X, a 6- to 10-membered ring, preferably a 6- to 8-membered ring.

In this respect, more detailed and preferred examples of structures R_(c)-R_(c) are given in Application WO 01/42258, page 7, line 11 to page 9, line 19, under the form “Rd¹-Rd²”.

In the context of the invention, the expression “independently represent” means that the designated substituents are either identical or different.

Preferred meanings of R₉ and R₁₂ are in particular a hydrogen atom; an alkyl group; an aryl group optionally substituted by alkyl; and a cycloalkyl group optionally substituted by alkyl.

For example, the diolefinic ligand L_(δ) of formula (IV) is symmetrical, that is to say that R₁₀═R₁₄; R₁₁═R₁₃; R₉═R₁₂ and the two groups Y₁ and Y₂ are either strictly identical to one another, or Y₁═CR_(a)R_(b) and Y₂═CR_(a)R_(b), or Y₁═SiR_(c)R_(d) and Y₂═SiR_(c)R_(d).

As regards the catalyst —C— of the composition according to the invention, mention should be made of a first particularly preferred group of metal complexes of following formula (I.1):

in which:

-   -   T₁ and T₂ are identical and are as defined above;     -   T₃ and T₄ are as defined above;     -   R_(c) and R_(d) are as defined above.

A second particularly preferred group of catalysts —C— of the composition according to the invention comprises the metal complexes of following formula (I.2):

in which:

-   -   T₁ and T₂ are identical and are as defined above;     -   T₃ and T⁴ are as defined above;     -   Z₃ to Z₆ are as defined above.

A third particularly preferred group of catalysts —C— of the composition according to the invention comprises the metal complexes of following formula (I.3):

in which:

-   -   T₁ and T₂ are identical and are as defined above;     -   T₃ and T₄ are as defined above;     -   and Z₁ and Z₂ are as defined above.

In addition to the catalyst —C—, the composition according to the invention comprises the two polyorganosiloxane entities reactive by polyaddition, namely the POS -A- and the POS —B—. The latter are chosen from the POSs composed of siloxyl units of general formula: (R²⁰)_(x)SiO_((4-x)/2)   (I′) and/or of siloxyl units of formula: (R²¹)_(y)(R²²)_(z)SiO_((4-y-z)/2)   (II′) in which formulae the various symbols have the following meanings:

-   -   the R²⁰ and R²² symbols, which are identical or different, each         represent a group with a nonhydrolysable hydrocarbonaceous         nature, it being possible for this radical to be:         -   an alkyl or haloalkyl radical having from 1 to 5 carbon             atoms and comprising from 1 to 6 chlorine and/or fluorine             atoms,         -   cycloalkyl and halocycloalkyl radicals having from 3 to 8             carbon atoms and comprising from 1 to 4 chlorine and/or             fluorine atoms,         -   aryl, alkylaryl and haloaryl radicals having from 6 to 8             carbon atoms and comprising from 1 to 4 chlorine and/or             fluorine atoms,         -   cyanoalkyl radicals having from 3 to 4 carbon atoms;     -   the R²¹ symbols, which are identical or different, each         represent a hydrogen atom, a C₂-C₆ alkenyl group, a hydroxyl         group, a hydrolysable atom or a hydrolysable group;     -   x=an integer equal to 0, 1, 2, or 3;     -   y=an integer equal to 0, 1, 2, or 3;     -   z=an integer equal to 0, 1 or 2;     -   the sum y+z is between 1 and 3;     -   with the condition according to which the Si-alkenyl POS -A-         comprises at least one unit R²¹=alkenyl per molecule and the         Si—H POS —B— comprises at least one unit R²¹=hydrogen per         molecule.

These POSs -A- and —B— are, for example, respectively a polyorganovinylsiloxane and a polyorganohydrosiloxane. The organic substituents, other than the vinyl reactive groups and the hydrogen, are, for example, methyls or phenyls. The hydrogens and the vinyls are carried by siloxyl units M=[R₃SiO—] and/or D=[-(R)₂SiO—] and/or T=[-(R)SiO—]. These hydrogenated or vinylated units M and D each comprise one or more H or vinyl units, preferably only one.

The number of SiH or SiVi units per molecule is at least equal to 2 and preferably at greater than 2.

This can represent from 0.01% to 10% (preferably 0.1 to 2%) of vinyl group (27 g/mol) by weight for the POS -A- and from 0.001% to 5% (preferably 0.05 to 2%) of hydrogen group (lg/mol) by weight for the POS —B—.

Generally, the POSs -A- and —B— which can be used in the reaction have an average molecular mass of between 1×10² and 1×10⁷ (g/mol).

For the POS -A-, this encompasses in particular, in terms of dynamic viscosity at 25° C., ranges:

-   -   of POSs which can be cured under hot conditions (HCE) by         polyaddition, having a viscosity at least equal to 1×10⁵ mPa·s,         preferably of between 1×10⁶ and 1×10⁷ mPa·s,     -   and of POSs which can be cured under hot conditions by         polyaddition, of liquid silicone elastomer (LSR) type, having a         viscosity preferably of between 1×10⁵ and 5×10⁵ mPa·s.

According to a preferred form of the invention, the silicone compositions concerned are POSs which can be cured under hot conditions (HCE) by polyaddition and in which the POSs -A- can have in practice a viscosity at 25° C. of, e.g., 2×10⁶ mPa·s and the POSs —B— of 10 to 5 000 mPa·s (e.g. 300 mPa·s).

In these examples, the viscosity is measured using a Brookfield viscometer according to the directions of the AFNOR Standard NFT 76 106 of May 82.

All the viscosities concerned in the present account correspond to a “Newtonian” dynamic viscosity quantity at 25° C., that is to say the dynamic viscosity which is measured, in a way known per se, at a shear rate gradient which is sufficiently low for the viscosity measured to be independent of the rate gradient.

The composition according to the invention can also comprise a certain number of conventional ingredients in addition to the POSs -A- and —B— and the catalyst —C—, including in particular at least one crosslinking inhibitor -D- capable of slowing down the polyaddition reaction and of making possible the storage of the single-component composition -A-B-C-D- in a not entirely crosslinked state.

The invention consequently relates to silicone compositions comprising at least one inhibitor -D- and in which the catalyst —C— is chosen from metal complexes of formula (I.1), formula (I.2), where Z3 to Z6 are devoid of electron-withdrawing residue(s), and formula (I.3), where Z1 and Z2 are devoid of electron-withdrawing residue(s). These compositions have long storage times (pot lives).

It should be noted that for some catalysts —C—, in particular those comprising a carbene (II) and at least one (preferably two) ligands L_(α) and L_(β) of formula (III.1) or (III.2), it is not necessary to use an inhibitor.

The invention is consequently also targeted at silicone compositions devoid of inhibitor -D- and in which the catalyst —C— is chosen from metal complexes:

-   -   of formula (I.2), where T₁, T₂, T₃, T₄, R_(c) and R_(d) are as         defined above and at least one of the Z³ to Z⁶ substituents         (preferably each substituent) comprises at least one         electron-withdrawing residue;     -   and/or of formula (I.3), where T₁, T₂, T₃ and T₄ are as defined         above and Z¹ and Z² are devoid of electron-withdrawing         residue(s).

These inhibitor-free compositions have, entirely advantageously and unexpectedly, long storage lives (pot lives) in an ambient atmosphere. Cross-linking only occurs under hot conditions. This advantage is a major one economically and with regard to convenience of use and of storage.

Advantageously, the inhibitors -D- (if they are employed) are selected from:

-   -   polyorganosiloxanes, advantageously cyclic polyorganosiloxanes,         substituted by at least one alkenyl,         tetramethylvinyl-tetrasiloxane being particularly preferred,     -   alkyl, alkenyl or alkynyl maleates, diallyl maleate being         particularly preferred,     -   acetylenic alcohols,     -   and/or alkyl, alkenyl or alkynyl acetylenedicarboxylates.

Such an inhibitor -D- is present in a proportion of at most 3 000 ppm, preferably in a proportion of 100 to 2 000 ppm, with respect to the total weight of the polyorganosiloxanes -A- and —B—.

Mention may be made, as conventional families of conventional functional additives capable of being employed in the silicone compositions according to the invention, of:

-   -   fillers,     -   hydroxylated POS oils of use as compatibilizer,     -   adhesion promoters,     -   adhesion modifiers,     -   pigments,     -   additives for stability towards heat, oils or fire (for example,         metal oxides).

The fillers optionally provided are preferably inorganic fillers. They can be composed of products chosen from siliceous materials which can act as reinforcing or semi-reinforcing filler.

Reinforcing siliceous fillers are chosen from colloidal silicas, fumed and precipitated silica powders, or their mixture.

Semi-reinforcing siliceous fillers, such as diatomaceous earths or ground quartz, can also be employed.

As regards nonsiliceous inorganic materials, they can be used as semi-reinforcing or bulking inorganic filler.

Examples of these nonsiliceous fillers, which can be used alone or as a mixture, are carbon black, titanium dioxide, aluminium oxide, alumina hydrate, expanded vermiculite, nonexpanded vermiculite, calcium carbonate, zinc oxide, mica, talc, iron oxide, barium sulphate and slaked lime.

Conveniently but without implied limitation, the fillers employed can be a mixture of quartz and silica.

The fillers can be treated with any appropriate product.

It is preferable, by weight, to employ an amount of filler of between 20 and 50, preferably between 25 and 35% by weight, with respect to the combined constituents of the composition.

More generally, the amounts in the compositions according to the invention are standard proportions in the technical field under consideration, it being understood that the targeted application also has to be taken into account.

According to another of its aspects, the present invention relates, as novel products, to the complexes of formula (I) as defined above, of use in particular as catalysts —C—.

The invention additionally relates to any catalytic composition comprising, as active material, one or more metal complexes of formula (I) as defined above.

Such catalysts (in particular hydrosilylation catalysts) have the distinctive characteristic that they can be formed in situ in silicone compositions of the type of those according to the invention, provided that the compositions comprise ligands L_(α) and L_(β) of formula (III.1) or (III.2), for example as inhibitor -D-. This or these ligands L_(α) and L_(β) of formula (III.1) or (III.2) are capable of displacing the initial ligands L_(δ) from the catalyst —C—. These are latent catalysts. The present invention obviously encompasses this scenario.

Another subject-matter of the invention is a process for the hydrosilylation of olefins or of acetylenic derivatives (for example, hydrosilylation of one or more POSs -A- using one or more POSs —B—), characterized in that it consists in employing the silicone composition as defined above and/or the catalytic composition also described above.

According to an advantageous alternative form in which recourse is had to at least one latent catalyst as described above, use is made of a silicone composition according to the invention as presented above comprising at least one inhibitor -D- which makes possible the in situ formation of at least one metal complex comprising at least one ligand L_(α) or L_(β) of formula (III.1) or (III.2).

The hydrosilylation reaction can be carried out in a solvent or in the absence of solvent. In an alternative form, one of the reactants can act as solvent: for example, the compound comprising an ethylenic double bond or comprising an acetylenic triple bond.

Appropriate solvents are solvents which are miscible with the compound comprising an Si—H unit.

Under the conditions of the hydrosilylation reaction, the catalyst complex must be dissolved in the reaction medium.

Examples of solvents which can be used for the hydrosilylation are in particular aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic or aromatic hydrocarbons, or ethers.

The hydrosilylation reaction can be carried out at a temperature of between 15° C. and 300° C., for example between 20 and 240° C.

Generally, the molar ratio of the unsaturations to the Si—H bonds varies between 1:100 and 10:1.

According to the invention, the hydrosilylation reaction is carried out in the presence of a catalytic amount of one or more complexes of formula (I). The term “catalytic amount” is understood to denote less than one molar equivalent of a metal choosen from the metals of group 8 with respect to the amount of unsaturations present in the reaction medium.

Generally, it is sufficient to introduce, into the reaction medium, less than 1 000 ppm, preferably less than 100 ppm, better still less than 50 ppm, of the metal of group 8, calculated with respect to the total mass of the unsaturated compound and of the compound comprising Si—H units.

As regards the preparation of the composition according to the invention, it relates to employing and mixing the compounds -A-, —B—, —C—, optionally -D- and one or more other conventional additives.

The mixing operations are entirely within the scope of a person skilled in the art.

The POSs -A- and —B—, the inhibitors -D- and the other conventional additives, such as fillers, are commodities fully available/accessible to a person skilled in the art.

As regards the metal complexes (I) forming the catalysts —C—, it has been seen above that the catalysts —C— comprising complexes:

with L_(α) and/or L_(β) of formula (III.1) or (III.2), can be obtained from complexes (I) in which L_(γ) is of formula (II) and L_(α) and L_(β) are of formula (IV), the latter being displaced in situ by inhibitors -D- of formula (III.1) or (III.2).

These complexes (I) in which L_(γ) is of formula (II) and L_(α) and L_(β) are of formula (IV) are prepared conventionally, for example from known complexes of the state of the art, by ligand exchange, that it to say by addition of the appropriate carbene of formula (II) to a metal complex of the metal M in solution, denoted precursor complex.

Appropriate precursor complexes are, for example, the Karstedt complex.

The complexes of formula (I) are generally prepared from precursor complexes exhibiting, as ligand, at least one diolefinic compound of formula (IV.P):

in which R₁, R₂, R₃, R₄, R₅, R₆, X, Y₁ and Y₂ are as defined above for the formula (I).

These ligands are either commercially available or are easily prepared by a person skilled in the art from commercial compounds. In this respect, reference may be made to the information given in Application WO 01/42258, more particularly page 15, line 1 to page 18, line 14.

The carbenes of formula (II) can be prepared by deprotonation of imidazolium salts, of tetrazolium salts, of triazolium salts or of pyrazolium salts, according to the situation, under the action of a base.

These reactions can be represented schematically as follows:

In these reaction schemes, T₁, T₂, T₃, T₄, A and B are as defined above for the formula (I) and X⁻ represents an anion.

The nature of the anion X⁻ is not critical according to the invention. The anion X⁻ is the anion derived from an organic or inorganic Brönsted acid (protic acid) . The anion X⁻ is usually derived from an acid exhibiting a pK_(a) of less than 6. Preferably, X⁻ derives from an acid with a pK_(a) of less than 4, better still of less than 2. The pK_(a) values concerned with here are the pK_(a) values of the acids as measured in water.

Examples of acids are sulphonic acids and phosphonic acids.

Mention will be made, as sulphonic acid, of benzenesulphonic acid and mention will be made, as phosphonic acid, of phenylphosphonic acid.

According to the invention, the anions X⁻ derived from the acids HCl, HBr, H₂SO₄, HBF₄ and H₃PO₄ are more particularly preferred.

The bases which can be used for the deprotonation of the salts of formula (VIII.1) are strong bases chosen from alkali metal hydrides, alkali metal carboxylates, alkali metal alkoxides and alkali metal amides.

Examples of appropriate bases are therefore sodium hydride, sodium methoxide, potassium tert-butoxide, lithium diisopropylamide and their mixtures.

The deprotonation reaction is preferably carried out in a solvent capable of at least partially dissolving the starting salt of formula (VIII.1) and the other reactants.

The nature of the solvent also depends on the strength of the base. This is because, in the case of a strong base and of particularly reactive starting salts, it may be necessary to operate at a low temperature.

Generally, the reaction temperature is between −78° C. and 40° C., preferably between −50 and 30° C., better still between −40 and 25° C., for example between −30 and 20° C.

Solvents which can be used in the process for the preparation of the carbenes are cyclic or noncyclic ethers.

Other preparation methods suitable for the synthesis of the carbenes of formula (II) are shown in Application WO 01/42258.

According to a particularly preferred embodiment of the invention, the metal complex of the invention has the formula:

in which L_(γ) is as defined above.

A simple method for the preparation of this complex consists in reacting the carbene L with the “conventional” Karstedt catalyst. This reaction can be carried out in bulk or in a solvent.

Examples of appropriate solvents are cyclic or noncyclic ethers, amides and aromatic hydrocarbons. The reaction temperature usually varies between 10 and 50° C. It is desirable to carry out the reaction in the presence of a slight excess of carbene with respect to the platinum.

Another advantageous preparation process consists in bringing together:

-   -   at least one salt of formula (VIII):

-   -   -   in which:         -   A, B, T₁, T₂, T₃ and T₄ are as defined above;         -   Z₇ independently represents an anion derived from a Brönsted             acid (protic acid),

    -   at least one appropriate precursor complex of formula (IV.P),

    -   at least one solvent (selected in particular from those         mentioned above),

    -   and at least one base (selected in particular from those         mentioned above).         In this respect, a detailed description of the latter process is         shown in French Application No. 01/07473, filed on 7 Jun. 2001.

The catalysts thus prepared can be used in hydrosilylation reactions. They make possible homogeneous catalysis of the reaction.

They also give access to single-component silicone compositions, preferably of polyaddition HCE type, exhibiting much longer pot lives than those prepared with conventional platinum-based catalysts, while using only very little or nothing in the way of inhibitors -D-.

The invention is illustrated in the light of the following examples.

EXAMPLES

The Pt-Carbene complexes used in the examples have the structures described below:

1. Synthesis of the Complex 2

The complex 2 was prepared according to the process disclosed in the document WO 01/42558.

2. Synthesis of the Complex 1

1,3-Bis(2-pyridyl)imidazolium chloride, used for the preparation of the complex 1, is synthesized according to the procedure described in the journal Organometallics, 2000, 19, 5113.

0.78 g of 1,3-bis(2-pyridyl)imidazolium chloride (3 mmol) and then 4.66 g of a Karstedt catalyst solution comprising 11.3% of Pt by weight (2.7 mmol of Pt) are introduced into a 250 ml reactor dried beforehand in an oven. 100 ml of anhydrous THF are subsequently added. 3.0 ml of 1M solution of t-BuOK in THF (3 mmol) are then injected over 30 min at 0° C.

The reaction mixture is stirred for an additional hour and then filtered and purified (conventional purification method).

3. Preparation of Crosslinkable Silicone Elastomer Composition

Each composition was prepared according to the following procedure:

An amount of catalyst equivalent to 67 ppm of Pt (calculated with respect to the total mass of vinylsiloxane oil and of hydrosiloxane oil) is dissolved in a few μl of toluene. 10 parts of an α,ω-vinylsiloxane oil, with a viscosity equal to 230 mPa·s and comprising 0.61% by mass of vinyl groups, are added to the solution. In example 3.1 no additional inhibitor is added. In example 3.2 a quantity of inhibitor (3,7,11-trimethyldodecyn-1-ol=TMDDO) is then added, if appropriate (Example 3.2), to produce the desired inhibitor/Pt molar ratio.

After rapid stirring, 2.7 parts of a hydrosiloxane oil, with a viscosity equal to 300 mPa·s and comprising 0.17% by mass of hydrogen, are added.

The DSC analyses of the preceding formulations are described below:

Temp. Peak of Begin- Temp. the Gelling Cata- Inhib- ning End exotherm time at lyst itor/Pt (° C.) (° C.) (° C.) 25° C. Example 3.1 1 / 106 122 114  30 days 3.2 1 60 150 163 154 >15 weeks Counter- example 1 2 / 95 123 107  1 day 2 2 60 152 177 164  13 weeks

The DSC curves and the gelling time at 25° C. show that the claimed complexes exhibit a satisfactory activity and result in more stable silicone compositions which can be crosslinked into elastomers. 

1. A silicone composition which is crosslinkable by hydrosilylation, said composition comprising at least one PolyOrganoSiloxane -A- (POS) carrying ethylenic and/or acetylenic unsaturation(s), at least one polyorganohydrosiloxane —B—, a metal catalyst —C— and optionally at least one inhibitor -D- of the hydrosilylation reaction; said catalyst —C— comprising at least one compound having the formula (I):

in which: M represents a metal of Group 8 of the Periodic Table; L_(γ) represents a carbene of formula (II):

in which: A and B, which are identical or different, represent C or N, it being understood that, when A represents N, then T₄ does not represent anything and, when B represents N, then T₃ does not represent anything; T₃ and T₄ independently represent a hydrogen atom; an alkyl group; a cycloalkyl group optionally substituted by alkyl or alkoxy; an aryl group optionally substituted by alkyl or alkoxy; an alkenyl group; an alkynyl group; or an arylalkyl group in which the aryl part is optionally substituted by alkyl or alkoxy; or T₃ and T₄ can together and with A and B, when the latter each represent a carbon atom, form an aryl; T₁ and T₂ independently represent an alkyl group; an alkyl group optionally substituted by alkyl; a perfluorinated alkyl group or an alkyl group optionally substituted by a perfluoroalkyl group; a cycloalkyl group optionally substituted by alkyl or alkoxy; an aryl group optionally substituted by alkyl or alkoxy; an alkenyl group; an alkynyl group; or an arylalkyl group in which the aryl part is optionally substituted by alkyl or alkoxy; or T₁ and T₂ independently represent a monovalent radical of following formula (V): V₁—V₂   (V)  in which: V₁ is a divalent hydrocarbonaceous radical, V₂ is a monovalent radical selected from the group consisting of the following substituents: alkoxy, —OR^(o) wherein R^(o) is hydrogen, alkyl or aryl, and amine; T₁ and T₂ independently represent a monovalent radical of following formula (W): W₁—ω—W₂   (W)  in which: W₁ is a divalent hydrocarbonaceous radical; ω represents: —R¹C═CR¹— wherein R¹ is H or alkyl, or —C≡C—; W₂ is a monovalent radical selected from the group consisting of the following substituents: R², which is alkyl or H; Si-alkyl or Si-alkoxy; alcohol; ketone; carboxyl; amide; and acyl; or the substituents T₁, T₂, T₃ and T₄ form in pairs, when they are situated at two adjacent points in the formula (II), a saturated or unsaturated hydrocarbonaceous chain; and with the condition that at least one substituent T₁ and/or T₂, which are identical or different, represent(s) a monovalent radical of following formula (V): Z₁-Z₂   (V) in which: Z₁ is a divalent hydrocarbonaceous radical, and Z₂ is a monovalent radical selected from the group consisting of: a (C₅—C₃₀)cycloalkyl radical having at least one heteroatom in the ring, and a (C₆—C₃₀)aryl radical having at least one heteroatom in the aromatic ring, L_(α) and L_(β) are ligands which are identical to or different from each other and each represent: Z¹—≡—Z²  (III.1)

 wherein, in these formulae (III.1) and (III.2): z¹, z², Z³, Z⁴, Z⁵ and Z⁶ each independently represent: hydrogen, halogen, cyano, or a saturated or unsaturated, electron-withdrawing or non-electron-withdrawing, hydrocarbonaceous group, or two vicinal Z₁ to Z₆ groups together form an electron-withdrawing or non-electron-withdrawing ring which optionally comprises heteroatoms; or L_(α) and L_(β) together form the ligand L_(δ) of formula (IV):

 in which: Y₁ and Y₂ represent, independently of each other, CR_(a)R_(b) or SiR_(C)R_(d); X represents O, NR_(e) or CR_(f)R_(g); R¹⁰, R¹¹, R¹³ and R¹⁴, which are identical or different, are selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group optionally substituted by alkyl; R⁹, R¹², R_(a), R_(b) and R_(e) are selected independently from the group consisting of a hydrogen atom; an alkyl group; an acyl group; an aryl group optionally substituted by alkyl; a cycloalkyl group optionally substituted by alkyl; and an arylalkyl group in which the aryl part is optionally substituted by alkyl; R_(c) and R_(d) are selected independently from the group consisting of alkyl; aryl optionally substituted by alkyl; cycloalkyl optionally substituted by alkyl; and arylalkyl in which the aryl part is optionally substituted by alkyl; or when Y₁ and Y₂ independently represent SiR_(c)R_(d), two R_(c) groups bonded to two separate silicon atoms together form a chain of the formula:

 in which n is an integer from 1 to 3; X is as defined above; R and R′, which are identical or different, have any one of the meanings given above for R_(e), it being understood that, when n is 2 or 3, only one silicon atom of the said chain may be substituted by one or two alkenyl or alkynyl groups; or when Y₁ and Y₂ independently represent SiR_(c)R_(d), two R_(c) groups bonded to separate silicon atoms together form a saturated hydrocarbonaceous chain, the two R_(c) groups forming, together with the said silicon atoms and X, a 6- to 10-membered ring; or when Y₁ and Y₂ independently represent CR_(a)R_(b), two R_(a) groups bonded to separate carbon atoms together form a saturated hydrocarbonaceous chain, the two R_(a) groups forming, together with the carbon atoms which carry them and X, a 6- to 10-membered ring; and R_(f) and R_(g) represent, independently of each other, a hydrogen atom; an alkyl group; an acyl group; an aryl group optionally substituted by alkyl; a cycloalkyl group optionally substituted by alkyl; an arylalkyl group in which the aryl part is optionally substituted by alkyl; a halogen atom; an alkenyl group; an alkynyl group; or an SiG₁G₂G₃ group where G₁, G₂ and G₃ are, independently of one another, alkyl; alkoxy; aryl optionally substituted by alkyl or alkoxy; or arylalkyl in which the aryl part is optionally substituted by alkyl or alkoxy.
 2. A composition according to claim 1, wherein M is Pt, Pd or Ni in the zero oxidation state.
 3. A composition according to claim 1, wherein in the formula (II): T₃ and T₄ represent a hydrogen atom or together form phenyl, and/or only one of T₁ or and T₂ represents (C₁—C₈)alkyl or (C₃—C₈)cycloalkyl, and/or A and B both represent a carbon atom.
 4. A composition according to claim 1, wherein in formulae (III.1) and (III.2), the electron-withdrawing groups are selected from the group consisting of:

in which: R₁₇, R₁₈, R₁₉ and R₂₀ are each a substituted or unsubstituted alkyl, alkenyl or alkynyl and n′ is between 1 and
 50. 5. A composition according to claim 1, wherein: Z₁, Z₂, Z₃, Z₄, Z₅ and Z₆ are selected from the group consisting of —COOCH₃, —COOCH₂CH₃, —CONC₁₂H₂₅ and —CN; or, wherein, when the Z₁ and Z₂ substituents form in pairs and with the triple bond, in (III.1), a ring Cy1 or wherein when Z₃ to Z₆ form in pairs, with or without the double bond, in (III.2), a ring Cy2, said rings Cy1 and Cy2 are independently selected from the group consisting of:


6. A composition according to claim 1, wherein L_(α) and L_(β) together form a ligand L_(δ) of formula (IV) in which Y₁ and Y₂ either both represent CR_(a)R_(b) or both represent SiR_(c)R_(d), so that the complexes have the formula (IV.1) or the formula (IV.2):

wherein the two R_(a) groups, the two R_(b) groups, the two R_(c) groups and the two R_(d) groups are identical to one another and R⁹ ═R₁₂; R₁₀ ═R₁₄; and R₁₁ ═R₁₃.
 7. A composition according claim 1, wherein the catalyst —C— has the formula (I.1):

in which: T₁ and T₂ are identical and are as defined in claim 13; T₃ and T₄ are as defined in claim 1; and and R_(c) and R_(d) are as defined in claim
 13. 8. A composition according to claim 1, wherein the POSs -A- and —B— are chosen from those composed of siloxyl units of the formula: (R²⁰)_(x)SiO_((4-x)/2)   (I′) and/or of siloxyl units of the formula: (R²¹)_(y)(R²²)_(z)SiO_((4-y-z)/2)   (II′) in which formulae the symbols have the following meanings: R₂₀ and R₂₂, which are identical or different, each represent a group with a nonhydrolyzable hydrocarbonaceous nature which is: an alkyl or haloalkyl radical having from 1 to 5 carbon atoms and having from 1 to 6 chlorine and/or fluorine atoms, a cycloalkyl or halocycloalkyl radical having from 3 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, an aryl, alkylaryl or haloaryl radical having from 6 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, or a cyanoalkyl radical having from 3 to 4 carbon atoms; R₂₁ represents a hydrogen atom, a C₂—C₆ alkenyl group, a hydroxyl group, a hydrolyzable atom or a hydrolyzable group, provided that when there are multiple R₂₁ groups, they are identical or different; x is an integer equal to 0,1, 2, or 3; y is an integer equal to 0,1, 2, or 3; z is an integer equal to 0, 1 or 2; and the sum y+z is from 1 to 3 inclusive; with the condition that the Si-alkenyl POS -A- comprises at least one unit R²¹═alkenyl per molecule and the Si—H POS —B— comprises at least one unit R²¹═hydrogen per molecule.
 9. The composition according to claim 1, wherein V₁ is alkylene and, when V₂ is an amine, it has the formula N(R_(o))₂ wherein R_(o) is hydrogen, alkyl or aryl.
 10. The composition according to claim 1, wherein W₁ is linear or branched C₁—C₁₀ alkylene, which is optionally substituted.
 11. The composition according to claim 1, wherein W₂ is alkyl, H, —Si(R₃)₃ wherein R₃ is alkyl, C(R₄)₂OH wherein R₄ is H or alkyl, —C(O)R₅ wherein R₅ is alkyl, —C(O)OR₆ wherein R₆ is alkyl, —C(O)N(R₇)₂ wherein R₇ is H or alkyl, or —OC(O)R₈ wherein R₈ is alkyl.
 12. The composition according to claim 1, wherein in formula (V), Z₁ is alkylene and Z₂ is (C₅—₃₀)cycloalkyl having at least one nitrogen atom in the ring or (C₆—C₃₀)aryl having at least one nitrogen atom in the aromatic ring.
 13. The composition according to claim 1, wherein in formula (III.1) and (III.2), when Z₁, Z₂, Z₃, Z₄, Z₅ and/or Z₆ is an unsaturated electron-withdrawing or non-electron-withdrawing, hydrocarbonaceous group, it is unsaturated adjacent to the double or triple bond.
 14. The composition according to claim 1, wherein in formulae (III.1) and (III.2), when two vicinal Z₁to Z₆ groups together form an electron-withdrawing or non-electron-withdrawing ring, said ring is other than the carbene L_(γ) of formula (II) and optionally has heteroatoms selected from the group consisting of O, N and S.
 15. The composition according to claim 2, wherein M is platinum in the zero oxidation state.
 16. The composition according to claim 3, wherein only one of T₁ and T₂ represents methyl, n-propyl, n-pentyl, cyclohexyl, adamantyl, allyl, methallyl, propargyl or homopropargyl.
 17. The composition according to claim 6, wherein X in formula (IV.1) and (IV.2) is an oxygen atom.
 18. The composition according to claim 1, wherein the POSs -A- and —B— are chosen from those composed of siloxyl units of the formula: (R²⁰)_(x)SiO_((4-x)/2)   (I′) and/or of siloxyl units of the formula: (R²¹)_(y)(R²²)_(z)SiO_((4-y-z)/2)   (II′) in which formulae the symbols have the following meanings: R₂₀ and R₂₂, which are identical or different, each represent a group with a nonhydrolyzable hydrocarbonaceous nature which is: an alkyl or haloalkyl radical having from 1 to 5 carbon atoms and having from 1 to 6 chlorine and/or fluorine atoms, a cycloalkyl or halocycloalkyl radical having from 3 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, an aryl, alkylaryl or haloaryl radical having from 6 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, or a cyanoalkyl radical having from 3 to 4 carbon atoms; R₂₁ represents a hydrogen atom, a C₂—C₆ alkenyl group, a hydroxyl group, a hydrolyzable atom or a hydrolyzable group, provided that when there are multiple R₂₁ groups, they are identical or different; x is an integer equal to 0,1, 2, or 3; y is an integer equal to 0,1, 2, or 3; z is an integer equal to 0, 1 or 2; and the sum y+z is from 1 to 3 inclusive; with the condition that the Si-alkenyl POS -A- comprises at least one unit R²¹═alkenyl per molecule and the Si—H POS —B— comprises at least one unit R²¹═hydrogen per molecule.
 19. The composition according to claim 2, wherein the POSs -A- and —B— are chosen from those composed of siloxyl units of the formula: (R²⁰)_(x)SiO_((4-x)/2)   (I′) and/or of siloxyl units of the formula: (R²¹)_(y)(R²²)_(z)SiO_((4-y-z)/2)   (II′) in which formulae the symbols have the following meanings: R²⁰ and R²², which are identical or different, each represent a group with a nonhydrolyzable hydrocarbonaceous nature which is: an alkyl or haloalkyl radical having from 1 to 5 carbon atoms and having from 1 to 6 chlorine and/or fluorine atoms, a cycloalkyl or halocycloalkyl radical having from 3 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, an aryl, alkylaryl or haloaryl radical having from 6 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, or a cyanoalkyl radical having from 3 to 4 carbon atoms; R²¹ represents a hydrogen atom, a C₂—C₆ alkenyl group, a hydroxyl group, a hydrolyzable atom or a hydrolyzable group, provided that when there are multiple R²¹ groups, they are identical or different; x is an integer equal to 0, 1, 2, or 3; y is an integer equal to 0, 1, 2, or 3; z is an integer equal to 0, 1 or 2; and the sum y+z is from 1 to 3 inclusive; with the condition that the Si-alkenyl POS -A- comprises at least one unit R²¹═alkenyl per molecule and the Si—H POS —B— comprises at least one unit R²¹═hydrogen per molecule.
 20. The composition according to claim 3, wherein the POSs -A- and —B— are chosen from those composed of siloxyl units of the formula: (R²⁰)_(x)SiO_((4-x)/2)   (I′) and/or of siloxyl units of the formula: (R²¹)_(y)(R²²)_(z)SiO_((4-y-z)/2)   (II′) in which formulae the symbols have the following meanings: R²⁰ and R²², which are identical or different, each represent a group with a nonhydrolyzable hydrocarbonaceous nature which is: an alkyl or haloalkyl radical having from 1 to 5 carbon atoms and having from 1 to 6 chlorine and/or fluorine atoms, a cycloalkyl or halocycloalkyl radical having from 3 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, an aryl, alkylaryl or haloaryl radical having from 6 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, or a cyanoalkyl radical having from 3 to 4 carbon atoms; R²¹ represents a hydrogen atom, a C₂—C₆ alkenyl group, a hydroxyl group, a hydrolyzable atom or a hydrolyzable group, provided that when there are multiple R²¹ groups, they are identical or different; x is an integer equal to 0, 1, 2, or 3; y is an integer equal to 0, 1, 2, or 3; z is an integer equal to 0, 1 or 2; and the sum y+z is from 1 to 3 inclusive; with the condition that the Si-alkenyl POS -A- comprises at least one unit R²¹═alkenyl per molecule and the Si—H POS —B— comprises at least one unit R²¹═hydrogen per molecule.
 21. The composition according to claim 4, wherein the POSs -A- and —B— are chosen from those composed of siloxyl units of the formula: (R²⁰)_(x)SiO_((4-x)/2)   (I′) and/or of siloxyl units of the formula: (R²¹)_(y)(R²²)_(z)SiO_((4-y-z)/2)   (II′) in which formulae the symbols have the following meanings: R²⁰ and R²², which are identical or different, each represent a group with a nonhydrolyzable hydrocarbonaceous nature which is: an alkyl or haloalkyl radical having from 1 to 5 carbon atoms and having from 1 to 6 chlorine and/or fluorine atoms, a cycloalkyl or halocycloalkyl radical having from 3 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, an aryl, alkylaryl or haloaryl radical having from 6 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, or a cyanoalkyl radical having from 3 to 4 carbon atoms; R²¹ represents a hydrogen atom, a C₂—C₆ alkenyl group, a hydroxyl group, a hydrolyzable atom or a hydrolyzable group, provided that when there are multiple R²¹ groups, they are identical or different; x is an integer equal to 0, 1, 2, or 3; y is an integer equal to 0, 1, 2, or 3; z is an integer equal to 0, 1 or 2; and the sum y+z is from 1 to 3 inclusive; with the condition that the Si-alkenyl POS -A- comprises at least one unit R²¹═alkenyl per molecule and the Si—H POS —B— comprises at least one unit R²¹═hydrogen per molecule.
 22. The composition according to claim 5, wherein the POSs -A- and —B— are chosen from those composed of siloxyl units of the formula: (R²⁰)_(x)SiO_((4-x)/2)   (I′) and/or of siloxyl units of the formula: (R²¹)_(y)(R²²)_(z)SiO_((4-y-z)/2)   (II′) in which formulae the symbols have the following meanings: R²⁰ and R²², which are identical or different, each represent a group with a nonhydrolyzable hydrocarbonaceous nature which is: an alkyl or haloalkyl radical having from 1 to 5 carbon atoms and having from 1 to 6 chlorine and/or fluorine atoms, a cycloalkyl or halocycloalkyl radical having from 3 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, an aryl, alkylaryl or haloaryl radical having from 6 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, or a cyanoalkyl radical having from 3 to 4 carbon atoms; R²¹ represents a hydrogen atom, a C₂—C₆ alkenyl group, a hydroxyl group, a hydrolyzable atom or a hydrolyzable group, provided that when there are multiple R²¹ groups, they are identical or different; x is an integer equal to 0, 1, 2, or 3; y is an integer equal to 0, 1, 2, or 3; z is an integer equal to 0, 1 or 2; and the sum y+z is from 1 to 3 inclusive; with the condition that the Si-alkenyl POS -A- comprises at least one unit R²¹═alkenyl per molecule and the Si—H POS —B— comprises at least one unit R²¹═hydrogen per molecule.
 23. The composition according to claim 6, wherein the POSs -A- and —B— are chosen from those composed of siloxyl units of the formula: (R²⁰)_(x)SiO_((4-x)/2)   (I′) and/or of siloxyl units of the formula: (R²¹)_(y)(R²²)_(z)SiO_((4-y-z)/2)   (II′) in which formulae the symbols have the following meanings: R²⁰ and R²², which are identical or different, each represent a group with a nonhydrolyzable hydrocarbonaceous nature which is: an alkyl or haloalkyl radical having from 1 to 5 carbon atoms and having from 1 to 6 chlorine and/or fluorine atoms, a cycloalkyl or halocycloalkyl radical having from 3 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, an aryl, alkylaryl or haloaryl radical having from 6 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, or a cyanoalkyl radical having from 3 to 4 carbon atoms; R²¹ represents a hydrogen atom, a C₂—C₆ alkenyl group, a hydroxyl group, a hydrolyzable atom or a hydrolyzable group, provided that when there are multiple R²¹ groups, they are identical or different; x is an integer equal to 0, 1, 2, or 3; y is an integer equal to 0, 1, 2, or 3; z is an integer equal to 0, 1 or 2; and the sum y+z is from 1 to 3 inclusive; with the condition that the Si-alkenyl POS -A- comprises at least one unit R²¹═alkenyl per molecule and the Si—H POS —B— comprises at least one unit R²¹═hydrogen per molecule.
 24. The composition according to claim 7, wherein the POSs -A- and —B— are chosen from those composed of siloxyl units of the formula: (R²⁰)_(x)SiO_((4-x)/2)   (I′) and/or of siloxyl units of the formula: (R²¹)_(y)(R²²)_(z)SiO_((4y-z)/2)   (II′) in which formulae the symbols have the following meanings: R²⁰ and R²², which are identical or different, each represent a group with a nonhydrolyzable hydrocarbonaceous nature which is: an alkyl or haloalkyl radical having from 1 to 5 carbon atoms and having from 1 to 6 chlorine and/or fluorine atoms, a cycloalkyl or halocycloalkyl radical having from 3 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, an aryl, alkylaryl or haloaryl radical having from 6 to 8 carbon atoms and having from 1 to 4 chlorine and/or fluorine atoms, or a cyanoalkyl radical having from 3 to 4 carbon atoms; R²¹ represents a hydrogen atom, a C₂—C₆ alkenyl group, a hydroxyl group, a hydrolyzable atom or a hydrolyzable group, provided that when there are multiple R²¹ groups, they are identical or different; x is an integer equal to 0, 1, 2, or 3; y is an integer equal to 0, 1, 2, or 3; z is an integer equal to 0, 1 or 2; and the sum y+z is from 1 to 3 inclusive; with the condition that the Si-alkenyl POS -A- comprises at least one unit R²¹═alkenyl per molecule and the Si—H POS —B— comprises at least one unit R²¹═hydrogen per molecule.
 25. A metal complex or catalyst comprising at least one compound having the formula (I):

in which: M represents a metal of Group 8 of the Periodic Table; L_(γ) represents a carbene of formula (II):

in which: A and B, which are identical or different, represent C or N, it being understood that, when A represents N, then T₄ does not represent anything and, when B represents N, then T₃ does not represent anything; T₃ and T₄ independently represent a hydrogen atom; an alkyl group; a cycloalkyl group optionally substituted by alkyl or alkoxy; an aryl group optionally substituted by alkyl or alkoxy; an alkenyl group; an alkynyl group; or an arylalkyl group in which the aryl part is optionally substituted by alkyl or alkoxy; or T₃ and T₄ can together and with A and B, when the latter each represent a carbon atom, form an aryl; T₁ and T₂ independently represent an alkyl group; an alkyl group optionally substituted by alkyl; a perfluorinated alkyl group or an alkyl group optionally substituted by a perfluoroalkyl group; a cycloalkyl group optionally substituted by alkyl or alkoxy; an aryl group optionally substituted by alkyl or alkoxy; an alkenyl group; an alkynyl group; or an arylalkyl group in which the aryl part is optionally substituted by alkyl or alkoxy; or T₁ and T₂ independently represent a monovalent radical of following formula (V): V₁—V₂   (V)  in which: V₁ is a divalent hydrocarbonaceous radical, V₂ is a monovalent radical selected from the group consisting of the following substituents: alkoxy, —OR^(o) wherein R^(o) is hydrogen, alkyl or aryl, and amine; T₁ and T₂ independently represent a monovalent radical of following formula (W): W₁—ω—W₂   (W)  in which: W₁ is a divalent hydrocarbonaceous radical; ω represents: —R¹C═CR¹— wherein R¹ is H or alkyl, or —C≡C—; W₂ is a monovalent radical selected from the group consisting of the following substituents: R², which is alkyl or H; Si-alkyl or Si-alkoxy; alcohol; ketone; carboxyl; amide; and acyl; or the substituents T₁, T₂, T₃ and T₄ form in pairs, when they are situated at two adjacent points in the formula (II), a saturated or unsaturated hydrocarbonaceous chain; and with the condition that at least one substituent T₁ and/or T₂, which are identical or different, represent(s) a monovalent radical of following formula (V): Z₁-Z₂   (V) in which: Z₁ is a divalent hydrocarbonaceous radical, and Z₂ is a monovalent radical selected from the group consisting of: a (C₅—C₃₀)cycloalkyl radical having at least one heteroatom in the ring, and a (C₆—C₃₀)aryl radical having at least one heteroatom in the aromatic ring, L_(α) and L_(β) are ligands which are identical to or different from each other and each represent:

 wherein, in these formulae (III.1) and (III.2): Z¹, Z², Z³, Z⁴, Z⁵ and Z⁶ each independently represent: hydrogen, halogen, cyano, or a saturated or unsaturated, electron-withdrawing or non-electron-withdrawing, hydrocarbonaceous group, or two vicinal Z¹ to Z⁶ groups together form an electron-withdrawing or non-electron-withdrawing ring which optionally comprises heteroatoms; or L_(α) and L_(β) together form the ligand L_(δ) of formula (IV):

 in which: Y₁ and Y₂ represent, independently of each other, CR_(a)R_(b) or SiR_(c)R_(d); X represents O, NR_(e) or CR_(f)R_(g); R¹⁰, R¹¹, R¹³ and R¹⁴, which are identical or different, are selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group optionally substituted by alkyl; R⁹, R¹², R_(a), R_(b) and R_(e) are selected independently from the group consisting of a hydrogen atom; an alkyl group; an acyl group; an aryl group optionally substituted by alkyl; a cycloalkyl group optionally substituted by alkyl; and an arylalkyl group in which the aryl part is optionally substituted by alkyl; R_(c) and R_(d) are selected independently from the group consisting of alkyl; aryl optionally substituted by alkyl; cycloalkyl optionally substituted by alkyl; and arylalkyl in which the aryl part is optionally substituted by alkyl; or when Y₁ and Y₂ independently represent SiR_(c)R_(d), two R_(c) groups bonded to two separate silicon atoms together form a chain of the formula:

 in which n is an integer from 1 to 3; X is as defined above; R and R′, which are identical or different, have any one of the meanings given above for R_(e), it being understood that, when n is 2 or 3, only one silicon atom of the said chain may be substituted by one or two alkenyl or alkynyl groups; or when Y₁ and Y₂ independently represent SiR_(c)R_(d), two R_(c) groups bonded to separate silicon atoms together form a saturated hydrocarbonaceous chain, the two R_(c) groups forming, together with the said silicon atoms and X, a 6- to 10-membered ring; or when Y₁ and Y₂ independently represent CR_(a)R_(b), two R_(a) groups bonded to separate carbon atoms together form a saturated hydrocarbonaceous chain, the two R_(a) groups forming, together with the carbon atoms which carry them and X, a 6- to 1 0-membered ring; and R_(f) and R_(g) represent, independently of each other, a hydrogen atom; an alkyl group; an acyl group; an aryl group optionally substituted by alkyl; a cycloalkyl group optionally substituted by alkyl; an arylalkyl group in which the aryl part is optionally substituted by alkyl; a halogen atom; an alkenyl group; an alkynyl group; or an SiG₁G₂G₃ group where G₁, G₂ and G₃ are, independently of one another, alkyl; alkoxy; aryl optionally substituted by alkyl or alkoxy; or arylalkyl in which the aryl part is optionally substituted by alkyl or alkoxy.
 26. A metal complex or catalyst according to claim 25, wherein M is Pt, Pd or Ni in the zero oxidation state.
 27. A metal complex according to claim 25, wherein L_(α) and L_(β) together form a ligand L_(δ) of formula (IV) in which Y₁ and Y₂ either both represent CR_(a)R_(b) or both represent SiR_(c)R_(d), so that the complexes have the formula (IV.1) or the formula (IV.2):

wherein the two R_(a) groups, the two R_(b) groups, the two R_(c) groups and the two R_(d) groups are identical to one another and R⁹═R¹²; R¹⁰═R¹⁴; and R¹¹═R¹³.
 28. A metal complex or catalyst according to claim 25, having the formula (I.1):

in which: T₁ and T₂ are identical and are as defined in claim 25; T₃ and T₄ are as defined in claim 25; and and R_(c) and R_(d) are as defined in claim
 25. 29. A process for the hydrosilylation of olefins or of acetylenic derivatives, said process comprising heating a composition according to claim 1 at about 100° C. or greater to crosslink its -A- and —B— polyorganosiloxane components.
 30. A process for the hydrosilylation of olefins or of acetylenic derivatives, said process comprising heating at least one PolyOrganoSiloxane -A- (POS) carrying ethylenic and/or acetylenic unsaturations and at least one polyorganohydrosiloxane —B—, in the presence of a metal complex or catalyst as defined in to claim 25 at about 100° C. or greater to crosslink said -A- and —B— components.
 31. The process according to claim 29, wherein the catalyst C in the composition comprises at least one ligand L_(α) or L_(β) of formula (III.1) or (III.2).
 32. The process according to claim 29, wherein the composition comprises at least one inhibitor -D- which is a ligand L_(α) or L_(β) of formula (III.1) or (III.2). 